WO2011160312A1

WO2011160312A1 - Degradable starch-based plastic masterbatch and preparation method thereof

Info

Publication number: WO2011160312A1
Application number: PCT/CN2010/074671
Authority: WO
Inventors: 孙彦升
Original assignee: Sun Yansheng
Priority date: 2010-06-23
Filing date: 2010-06-29
Publication date: 2011-12-29
Also published as: CN101851355A; CN101851355B; EP2586821B1; EP2586821A1; EP2586821A4

Abstract

Degradable starch-based plastic masterbatch and preparation method thereof are provided. The degradable starch-based plastic masterbatch is prepared from the following raw materials in parts by weight: 40 to 70 parts of starch, 10 to 20 parts of light calcium carbonate, 2 to 10 parts of fine aggregate, 13 to 25 parts of plastic material, 1 to 5 parts of compatilizer, 1 to 5 parts of lubricant, 1 to 5 parts of modifier and 1 to 5 parts of degradation promoter. The light calcium carbonate and the fine aggregate are added into the degradable starch-based plastic masterbatch, so that the addition amount of synthetic polymers is reduced; and through the preparation under the reasonable process condition, the quality of the product is improved, and the cost is reduced by 45 percent on the premise of ensuring the degradation effect.

Description

Degradable starch-based plastic masterbatch and preparation method thereof

The invention relates to the technical field of biodegradation, in particular to a degradable starch-based plastic masterbatch and a preparation method thereof.

Background technique

Plastics are widely used in many fields due to their light weight, high strength, stable chemical properties and low cost. The plastics industry has developed rapidly, and the used plastics have not been properly treated. Plastic waste brings serious pollution to the natural environment. Discarding plastic waste can pollute the environment. Deep burial will encroach on the land. Burning will pollute the air. The fundamental way to solve the problem is to develop a degradable plastic instead of non-degradable plastic.

Environmentally-degradable plastics are a new class of plastics. The development of environmentally-degradable plastics in foreign countries began in the 1970s, when light-degradable plastics were mainly developed to solve the environmental pollution problems caused by plastic waste, especially disposable plastic packaging products. By the 1980s, development research turned to biodegradable plastics, and there were also biodegradable plastics produced from renewable materials such as plant starch and cellulose, animal chitin, etc. without using petroleum. The research and development of degradable plastics in China is basically the same as in the world. However, research and development of degradable plastics in China began with agricultural mulch. China is a large agricultural country, and the consumption of mulch film ranks first in the world. In order to solve the damage caused by the residual mulch accumulated in farmland to the root development of plants, the crop yield is affected, and the residual film is hindered by the operation of agricultural machinery. There is a biodegradable plastic filled with starch in general-purpose plastics. At the same time, on the basis of photodegradable plastics, a mulch film which simultaneously fills starch and has both photodegradation and biodegradation functions is developed. In recent years, with the improvement of people's living standards, the use of disposable plastic packaging products has increased, and the resulting environmental pollution problems have become increasingly serious. To this end, according to different uses and environmental conditions, the development of a punctual and controllable environment Degrading plastics has become an urgent problem to be solved.

Summary of the invention

The object of the present invention is to provide a degradable starch-based plastic masterbatch, which is promoted by starch, light calcium carbonate, stone powder, plastic material, compatibilizer, lubricant, modifier and degradation. The agent is used as a raw material and is prepared under reasonable process conditions to obtain an easily controllable degradation and conforming to the product. A plastic masterbatch with reduced strength and flexibility and low processing cost.

Another object of the present invention is to provide a process for preparing a degradable starch-based plastic masterbatch.

The object of the present invention is achieved by the following technical solutions: A degradable starch-based plastic masterbatch prepared from the following raw materials in parts by weight:

Starch 40' -70

Light calcium carbonate lO ~20

Stone powder 2~ 0

Plastic material 13- -25

Compatibilizer 1~5

Lubricant 1~ -5

Modifier 1~ ^5

Degradation accelerator 1~5 ;

The plastic material is polypropylene, polypropylene resin or linear polyethylene.

Further, the degradable starch-based plastic masterbatch is prepared from the following raw materials in parts by weight:

Starch 65

Light calcium carbonate 7

Stone powder 3

Plastic materials 15

Compatibilizer 2

Lubricant 2

Modifier 3

Degradation accelerator 3 o

Starch 40

20

Stone powder 3 Compatibilizer 2

Lubricant 2

Modifier 3

Degradation accelerator 5.

The starch is corn native starch or tapioca starch.

The stone powder is talc powder or jade powder.

The compatibilizer is one of a vegetable oil, a mineral oil, an aluminate coupling agent, or a mixture thereof.

The lubricant is a polyethylene wax.

The modifier is itaconic acid.

The degradation promoter is epoxidized soybean oil.

A preparation method of a degradable starch-based plastic masterbatch, the preparation steps of which are as follows:

A, weighing the components according to the weight ratio of the raw materials;

B. Put starch, light calcium carbonate and stone powder in a mixer, and mix and stir for 20-30 minutes under the temperature of 165-18CTC;

C, adding a modifier, mixing and stirring at 140-155 ° C for 2-6 minutes;

D, adding a compatibilizer, mixing and stirring at 140-16CTC temperature for 4-6 minutes;

E, adding plastic materials, degradation promoters and lubricants, mixing and stirring at 160-175 ° C for 10-12 minutes, and then placing the mixture materials in a holding container for cooling to obtain a mixed base;

F. The obtained mixed base is placed in a granulation apparatus for granulation to obtain the degradable starch-based plastic masterbatch, and the granulation apparatus has a temperature of 120 to 170 °C.

Compared with the prior art, the invention has the following advantages:

1. The degradable starch-based plastic masterbatch of the invention uses starch as a biologically active substance, and adds light, oxygen and thermal degradation promoters, and has multiple degradation characteristics under the action of light, oxygen, heat and microorganisms. Moreover, after the degradation process is in the induction period (controllable), the masterbatch and its products lose their original performance, the mechanical properties drop sharply, and then degrade into fragments and powders, and finally assimilate with the environment. Compared with the prior art, the molecular weight of the synthetic polymer is significantly reduced, and the degradation can continue in an aerobic environment, eventually producing carbon dioxide and water, and not causing secondary pollution after entering the air and soil. Degradation cycle (induction period) can be seen as needed 2. The surface of the mulch film blown by the degradable starch-based plastic masterbatch of the invention is smooth and evenly distributed, and the light transmittance is ≥70%; the degradation period can be controlled within 2-8 months.

3. A plastic film produced by using the degradable starch-based plastic masterbatch of the present invention has better flexibility and strength in accordance with product requirements. The transverse/longitudinal tensile force of the plastic film was 1. 2 N, and the elongation at break was 115%.

4. The degradable starch-based plastic masterbatch of the invention is added with light calcium carbonate and stone powder, which greatly reduces the amount of synthetic polymer (polypropylene, polypropylene resin or linear polyethylene), and is prepared by reasonable process conditions. Not only improved product quality, but also reduced the cost by 45% under the premise of ensuring degradation. detailed description

The present invention will be further described below in conjunction with the embodiments.

A degradable starch-based plastic masterbatch prepared from the following raw materials in parts by weight: starch 40 - 70

Light calcium carbonate lO -20

Stone powder 2~ 0

Plastic material 13- -25

Compatibilizer 1~5

Lubricant 1~5

Modifier 1~5

Degradation accelerator 1~5 ;

The various raw materials described above can be purchased from manufacturers and chemical stores, and their specifications and quality meet national or industry standards.

In the above raw materials of the present invention, the starch may be corn raw starch or tapioca starch. The stone powder may be talc or jade powder; the jade powder is usually used in the preparation of a plastic masterbatch of a high-end end product. The compatibilizing agent may be one of a vegetable oil (such as: castor oil), a mineral oil (such as: white mineral oil), an aluminate coupling agent, or a mixture thereof; when the end product is used for packaging or contacting food, The compatibilizer is preferably a vegetable oil. The lubricant is a polyethylene wax. The modifier is Itacomc Acid, and the scientific name is methylene succinic acid (molecular formula: C ₅ H ₆ 0 ₄ ). The degradation promoter is epoxidized soybean oil.

Further, a degradable starch-based plastic masterbatch prepared from the following raw materials in parts by weight Made of:

Starch 65

Light calcium carbonate 7

Stone powder 3

Plastic materials 15

Compatibilizer 2

Lubricant 2

Modifier 3

Degradation accelerator 3.

Example 1 : A degradable starch-based plastic masterbatch of the present embodiment is prepared from the following raw materials in proportion by weight:

Corn native starch 65

Light calcium carbonate 7

Talc powder 3

Polypropylene resin 15

Aluminate coupling agent 2

Polyethylene wax 2

Itaconic acid 3

Epoxidized soybean oil 3.

In the present embodiment, the light calcium carbonate can increase the flexibility of the product, and when used in the manufacture of a plastic mulch or a plastic bag, the product can be fluffy, and has good light transmittance, ductility and flexibility.

Talc powder can increase the strength of the product, that is, it has sufficient load carrying capacity under the condition that the end product is light, thin, and has good light transmittance and flexibility.

The preparation method of the degradable starch-based plastic masterbatch is exemplified by the production of 100 kg of the product, and the preparation steps are as follows:

A. The components are weighed according to the weight ratio of the raw materials; wherein, the moisture content of the raw materials of corn raw starch, light calcium carbonate and talc is less than 6%.

B. Put 65kg of corn original starch, 7kg of light calcium carbonate and 3kg of talcum powder in a mixer. Mix and stir at 165-180 ° C for 20-30 minutes.

The mixer of this embodiment is a heating/cooling mixer of the type SRL-230/500A (specification: hot mixing 300 L / cold mixing 500 L).

C. Add 3 kg of the modifier itaconic acid and mix and stir for 4 minutes at 148 °C.

D. Add 2 kg of compatibilizer aluminate coupling agent and mix and stir for 5 minutes at 15CTC.

E. Add 15kg of polypropylene resin, 3kg of degradation accelerator epoxidized soybean oil and 2kg of lubricant polyethylene wax, mix and stir for 12 minutes at 167 °C, then place the mixture in a container to cool. Mix the base.

F. The obtained mixed base material is placed in a granulation apparatus for granulation to obtain the degradable starch-based plastic masterbatch; the product plastic masterbatch has a diameter of 2 mm and a length of 3-4 mm, and is cylindrical.

The granulating apparatus used in the step F of the present embodiment is a parallel twin-screw granulating unit of the type TE-65 (specification: screw length to diameter ratio of 44:1, rotation speed of 30-500 rpm); the parallel twin-screw granulation The temperature of each section of the twin screw of the unit is 120-170 °C.

The parameters of the degradable starch-based plastic masterbatch obtained by the preparation method of the present invention are as follows:

(1) Moisture content: < 1%;

(2) Melt index: l-3g/10min;

(3) Specific gravity: 1-1. 2g/cm ³ .

The degradable starch-based plastic masterbatch of the present embodiment can be used for blowing into an agricultural mulch film, a packaging film, a food bag, a fresh-keeping bag, a garbage bag, etc. according to a conventional method. Wherein, the degradable starch-based plastic masterbatch of the present invention is added to the synthetic polymer plastic in the amount of the blown mulch film or the packaging film masterbatch, as the case may be.

30 wt%, blown at a temperature of 160 ° C to 200 ° C using a conventional blown film apparatus. The surface of the blown film or packaging film is smooth, evenly distributed, and the light transmittance is ≥70%. After testing, the degradation cycle of the prepared mulch film or packaging film can be controlled to about 3 months, and degradation begins after 3 months, without any residue after complete degradation. Example 2: A degradable starch-based plastic masterbatch of the present embodiment is prepared from the following raw materials according to their weight: parts ratio:

Corn native starch 40

Light calcium carbonate 20

Talc powder 3

Polypropylene resin 25

Aluminate coupling agent 2

Polyethylene wax 2

Itaconic acid 3

Epoxidized soybean oil 5.

B. Place 40 kg of corn original starch, 20 kg of light calcium carbonate, and 3 kg of talc in a mixer, and mix and stir for 20-30 minutes under the temperature of 165-18 CTC.

C. Add 3 kg of the modifier itaconic acid and mix and stir for 5 minutes at 150 °C.

E. Add 25kg of polypropylene resin, 5kg of degradation accelerator epoxy soybean oil and 2kg of lubricant polyethylene wax, mix and stir for 10 minutes at 17CTC temperature, then place the mixture in a container to cool, to obtain mixed base. material.

The degradable starch-based plastic masterbatch of the present embodiment can be used for blowing into an agricultural mulch film, a packaging film, a food bag, a fresh-keeping bag, a garbage bag, etc. according to a conventional method. Wherein, in the case of the blown mulch film or the packaging film masterbatch, the 20% by weight of the degradable starch-based plastic masterbatch of the invention is added to the synthetic polymer plastic, and the ordinary blown film device is used at a temperature of 150 ° C. Blow at -200 °C. The surface of the blown film or packaging film is smooth, evenly distributed, and the light transmittance is ≥70%. Tested, prepared mulch or packaging The degradation cycle of the membrane can be controlled for about 8 months, and degradation begins after 8 months, without any residue after complete degradation.

Example 3: A degradable starch-based plastic masterbatch of the present embodiment is prepared from the following raw materials in terms of their weight ratio:

Corn native starch 70

Light calcium carbonate 10

Talc powder 2

Polypropylene resin 13

Aluminate coupling agent 1

Polyethylene wax 1

Itaconic acid 1

Epoxidized soybean oil 2.

B. Put 70 kg of corn original starch, 10 kg of light calcium carbonate, and 2 kg of talc in a mixer, and mix and stir for 20-30 minutes under the temperature of 165-18 CTC.

C. Add 1 kg of the modifier itaconic acid, and mix and stir for 3 minutes at 155 °C;

D, adding a compatibilizer aluminate coupling agent 1 kg, mixing and stirring at 155 ° C for 3 minutes;

E. Add 13 kg of polypropylene resin, 2 kg of degradation accelerator epoxidized soybean oil and lubricant polyethylene wax lkg, mix and stir at 175 °C for 10 minutes, then place the mixture in a container to cool. Mixed base material;

The degradable starch-based plastic masterbatch of the present embodiment can be used for blowing into an agricultural mulch film, a packaging film, a food bag, a fresh-keeping bag, a garbage bag, etc. according to a conventional method. Wherein, the degradable starch-based plastic masterbatch of the invention is added to the synthetic polymer plastic according to the situation and needs of the blown mulch film or the packaging film masterbatch. 40 wt%, blown at a temperature of 170 ° C to 200 ° C using a conventional blown film apparatus. The surface of the blown film or packaging film is smooth, evenly distributed, and the light transmittance is ≥70%. After testing, the degradation cycle of the prepared mulch film or packaging film can be controlled to about 4 months, and degradation begins after 4 months, without any residue after complete degradation.

The degradable starch-based plastic masterbatch of the present invention can be used to prepare a container having a fixed shape (e.g., a bottle, etc.) according to a conventional method. 100% by weight of degradable starch-based plastic masterbatch is used in the preparation of the container. According to the requirements of the terminal product, the degradation cycle of the container can be controlled to about 6-18 months, and degradation starts after 6-18 months, and there is no residue after complete degradation.

Claims

Request

A degradable starch-based plastic masterbatch characterized in that it is prepared from the following raw materials in parts by weight:

Starch 40 -70

Light calcium carbonate lO -20

Stone powder 2~ 0

Plastic material 13- -25

Compatibilizer 1~5

Lubricant 1~5

Modifier 1~5

Degradation accelerator 1~5 ;

The plastic material is polyacryl, polypropylene resin or linear polyethylene.

The degradable starch-based plastic masterbatch according to claim 1, which is prepared from the following raw materials in parts by weight:

Starch 65

Light carbonized surface 7

Stone powder 3

Plastic materials 15

Compatibilizer 2

Lubricant 2

Modifier 3

Degradation accelerator 3 o

Starch 40

Lightweight 20

Stone powder 3

Plastic materials 25

2 Lubricant 2

Modifier 3

Degradation accelerator 5.

The degradable starch-based plastic masterbatch according to claim 1, 2 or 3, wherein the starch is corn raw starch or tapioca starch.

The degradable starch-based plastic masterbatch according to claim 1, 2 or 3, wherein the stone powder is talc powder or jade powder.

The degradable starch-based plastic masterbatch according to claim 1, 2 or 3, wherein the compatibilizing agent is one of vegetable oil, mineral oil, aluminate coupling agent or a mixture thereof.

The degradable starch-based plastic masterbatch according to claim 1, 2 or 3, wherein the lubricant is a polyethylene wax.

The degradable starch-based plastic masterbatch according to claim 1, 2 or 3, wherein the modifier is itaconic acid.

The degradable starch-based plastic masterbatch according to claim 1, 2 or 3, wherein the degradation promoter is epoxidized soybean oil.

10. A method for preparing a degradable starch-based plastic masterbatch, characterized in that the preparation steps are as follows:

A, weighing the components according to the weight ratio of the raw materials;

C, adding a modifier, mixing and stirring at 140-155 ° C for 2-6 minutes;